amino acids, peptides, and proteinsihara/seimei/c22-2015s.pdfchapter 22 amino acids, peptides, and...
TRANSCRIPT
Chapter 22
Amino Acids, Peptides, and Proteins
p.1127
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Peptide ondg
Amino acid Uri8KO�
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p.1132
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p.1129 jvz
p.1129 yV\z
p.1130 V`yV\z
p.1130 _vz
p.1130 fxXhz
p.1130 \^eVz
p.1130 sdXhz
p.1130 U^kuZz8
p.1130 U^kuZz
p.1130 [wbrz8
p.1130 [wbrz
p.1130 v\z�
p.1131 l^d]z�
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p.1131 fvnfmTz�
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p.1131 UwZhz�
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p.1131 mWhwUuhz�
p.1131 dy\z�
p.1131 nyvz�
pKa Uri8N3=$�O
83=��J%3GQC
=5,K,=69,N)��
54A@A5/AnA40A�
�&��69OB69A3A75/87408,1,7548A>
0;<:,69,3,0;<:-75/87408,1,7548.>
0;<:,69,3,0;<:75/8,/,0;<:-740817548.>
=5,3,0;<:75/8,B=5,3,0;<:75/8,BK�#HRKB>
=69,3,=5,0,;<:-740817548.�
�?A7408p7548,N�B,;<:-740817548.p2�
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
0.79
SULFINIC & SULFONIC ACIDSPEROXIDES
pKa (DMSO)(DMSO)pKapKa (DMSO)
pKa's of Inorganic and Oxo-Acids
8.2
11.5
12.5
15.5
15.7
(11.1)
(12.3)
(1.6)
(0.3)-14
(7.9)
(12.9)
(15)
(1.8)
(0.9)
(32)
(DMSO)
cis-CO2H
trans-CO2H
R=
3.6, 10.3
3.77
-0.25
0.65
1.29
-8.0
11.6
-3.0, 1.99
1.9, 7.21
4.00
2.12, 7.21,12.32
7.00
-1.7
15.7
-1.3
3.29
4.72
9.24
3.17
-0.98, 6.50
9.4
-2.6
-10
7.5
-9.00
9.23
INORGANIC ACIDS
Chem 206
SubstrateSubstrate
+
+
1.92, 6.23
-12.4
-7.8
-6.2
-3.8
-2.05
-2.2
-2.6
2.1
+
-1.8
-6.5
X=
1.68
2.66
2.86
2.86
3.12
4.76
4.2
o-O2NC6H4
m-O2NC6H4
p-O2NC6H4
o-(CH3)3N+C6H4
p-OMeC6H4
p-ClC6H4
o-ClC6H4
m-ClC6H4
2.17
2.45
3.44
2.94
3.83
3.99
1.37
p-(CH3)3N+C6H43.43
4.47
4.25
3.02, 4.38
Substrate Substrate
(13.7)
(18.5)
PROTONATED SPECIESCARBOXYLIC ACIDS
(31.2)
(27.9)
(29.3)
(23.5)
(18.2)
(29.4)
10.2
7.1
8.4
p-OMeC6H4OH
p-O2NC6H4OH
m-O2NC6H4OH
9.95 (18.0)
2-napthol (17.1)
(10.8)
(19.1)
ALCOHOLS
16.5
17.0
c-hex3COH 24.0
OXIMES & HYDROXAMIC ACIDS
8.88
11.3 (20.1)
pKa
O
OHR
PhPh
NOH
NH
PhOH
N+
O
OH
O+
H
HMe
NOH
Ph
O
Me
O
OHX
MeO+
Me
N+
O
OHPh
OH
OHPh
Ph CH3
OH
O+
H
H
MeS
OH
O O
PhS
OH
O
S
OH
MeMe
O+
H
MePh
For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
H2OH2OH2O
CH3CO3H
MeOOH
CF3SO3H
(CF3)2CHOH
CF3CH2OH
t-BuOH
MeOH
HOH
H
HO
H
CF3
CCl3
CHCl2
HOOH
H2SO4
H2SO3
HSCN
H3PO4
H2S
H3O+
H2O
HNO3
HNO2
HN3
NH4Cl
H2CrO4
HCN
CH3SO3H
HClO4
HOCl
HF
HCl
HBr
B(OH)3
CH2NO2
CH2F
CH2Cl
CH2Br
CH2I
CH3
C6H5
i-PrOH
C6H5OH
(NH)
H2O
9.3
(+5.55)N OHMe
Me
Me
(+1.63)
pKa Table.1 11/4/05 1:43 PM
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
0.79
SULFINIC & SULFONIC ACIDSPEROXIDES
pKa (DMSO)(DMSO)pKapKa (DMSO)
pKa's of Inorganic and Oxo-Acids
8.2
11.5
12.5
15.5
15.7
(11.1)
(12.3)
(1.6)
(0.3)-14
(7.9)
(12.9)
(15)
(1.8)
(0.9)
(32)
(DMSO)
cis-CO2H
trans-CO2H
R=
3.6, 10.3
3.77
-0.25
0.65
1.29
-8.0
11.6
-3.0, 1.99
1.9, 7.21
4.00
2.12, 7.21,12.32
7.00
-1.7
15.7
-1.3
3.29
4.72
9.24
3.17
-0.98, 6.50
9.4
-2.6
-10
7.5
-9.00
9.23
INORGANIC ACIDS
Chem 206
SubstrateSubstrate
+
+
1.92, 6.23
-12.4
-7.8
-6.2
-3.8
-2.05
-2.2
-2.6
2.1
+
-1.8
-6.5
X=
1.68
2.66
2.86
2.86
3.12
4.76
4.2
o-O2NC6H4
m-O2NC6H4
p-O2NC6H4
o-(CH3)3N+C6H4
p-OMeC6H4
p-ClC6H4
o-ClC6H4
m-ClC6H4
2.17
2.45
3.44
2.94
3.83
3.99
1.37
p-(CH3)3N+C6H43.43
4.47
4.25
3.02, 4.38
Substrate Substrate
(13.7)
(18.5)
PROTONATED SPECIESCARBOXYLIC ACIDS
(31.2)
(27.9)
(29.3)
(23.5)
(18.2)
(29.4)
10.2
7.1
8.4
p-OMeC6H4OH
p-O2NC6H4OH
m-O2NC6H4OH
9.95 (18.0)
2-napthol (17.1)
(10.8)
(19.1)
ALCOHOLS
16.5
17.0
c-hex3COH 24.0
OXIMES & HYDROXAMIC ACIDS
8.88
11.3 (20.1)
pKa
O
OHR
PhPh
NOH
NH
PhOH
N+
O
OH
O+
H
HMe
NOH
Ph
O
Me
O
OHX
MeO+
Me
N+
O
OHPh
OH
OHPh
Ph CH3
OH
O+
H
H
MeS
OH
O O
PhS
OH
O
S
OH
MeMe
O+
H
MePh
For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
H2OH2OH2O
CH3CO3H
MeOOH
CF3SO3H
(CF3)2CHOH
CF3CH2OH
t-BuOH
MeOH
HOH
H
HO
H
CF3
CCl3
CHCl2
HOOH
H2SO4
H2SO3
HSCN
H3PO4
H2S
H3O+
H2O
HNO3
HNO2
HN3
NH4Cl
H2CrO4
HCN
CH3SO3H
HClO4
HOCl
HF
HCl
HBr
B(OH)3
CH2NO2
CH2F
CH2Cl
CH2Br
CH2I
CH3
C6H5
i-PrOH
C6H5OH
(NH)
H2O
9.3
(+5.55)N OHMe
Me
Me
(+1.63)
pKa Table.1 11/4/05 1:43 PM
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
0.79
SULFINIC & SULFONIC ACIDSPEROXIDES
pKa (DMSO)(DMSO)pKapKa (DMSO)
pKa's of Inorganic and Oxo-Acids
8.2
11.5
12.5
15.5
15.7
(11.1)
(12.3)
(1.6)
(0.3)-14
(7.9)
(12.9)
(15)
(1.8)
(0.9)
(32)
(DMSO)
cis-CO2H
trans-CO2H
R=
3.6, 10.3
3.77
-0.25
0.65
1.29
-8.0
11.6
-3.0, 1.99
1.9, 7.21
4.00
2.12, 7.21,12.32
7.00
-1.7
15.7
-1.3
3.29
4.72
9.24
3.17
-0.98, 6.50
9.4
-2.6
-10
7.5
-9.00
9.23
INORGANIC ACIDS
Chem 206
SubstrateSubstrate
+
+
1.92, 6.23
-12.4
-7.8
-6.2
-3.8
-2.05
-2.2
-2.6
2.1
+
-1.8
-6.5
X=
1.68
2.66
2.86
2.86
3.12
4.76
4.2
o-O2NC6H4
m-O2NC6H4
p-O2NC6H4
o-(CH3)3N+C6H4
p-OMeC6H4
p-ClC6H4
o-ClC6H4
m-ClC6H4
2.17
2.45
3.44
2.94
3.83
3.99
1.37
p-(CH3)3N+C6H43.43
4.47
4.25
3.02, 4.38
Substrate Substrate
(13.7)
(18.5)
PROTONATED SPECIESCARBOXYLIC ACIDS
(31.2)
(27.9)
(29.3)
(23.5)
(18.2)
(29.4)
10.2
7.1
8.4
p-OMeC6H4OH
p-O2NC6H4OH
m-O2NC6H4OH
9.95 (18.0)
2-napthol (17.1)
(10.8)
(19.1)
ALCOHOLS
16.5
17.0
c-hex3COH 24.0
OXIMES & HYDROXAMIC ACIDS
8.88
11.3 (20.1)
pKa
O
OHR
PhPh
NOH
NH
PhOH
N+
O
OH
O+
H
HMe
NOH
Ph
O
Me
O
OHX
MeO+
Me
N+
O
OHPh
OH
OHPh
Ph CH3
OH
O+
H
H
MeS
OH
O O
PhS
OH
O
S
OH
MeMe
O+
H
MePh
For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
H2OH2OH2O
CH3CO3H
MeOOH
CF3SO3H
(CF3)2CHOH
CF3CH2OH
t-BuOH
MeOH
HOH
H
HO
H
CF3
CCl3
CHCl2
HOOH
H2SO4
H2SO3
HSCN
H3PO4
H2S
H3O+
H2O
HNO3
HNO2
HN3
NH4Cl
H2CrO4
HCN
CH3SO3H
HClO4
HOCl
HF
HCl
HBr
B(OH)3
CH2NO2
CH2F
CH2Cl
CH2Br
CH2I
CH3
C6H5
i-PrOH
C6H5OH
(NH)
H2O
9.3
(+5.55)N OHMe
Me
Me
(+1.63)
pKa Table.1 11/4/05 1:43 PM
"��MQRpKaN� �
9-7
���.� � Inductive Effect
/�
pKa
4.8
2.8
4.1
4.5
4.7
"
.� � ��+*������Delocalization of Negative Charge
by Inductive Effect
2.6
Cl CH2 C
O
O
1.3
0.7
OH OHO2N
OOO O
O
NO
O
O
NO
O
*9.5. *# ��"��������Electronic Effect
/��
pKa 10 7.2
%����!&$�(Canonical Formulae)
�' �������
����, � Resonance Effect
�������!&$�(Canonical Formulae) �
' �������
1.0�-"�pKa 4.6
/��NH2 NH2O2N
NH2
NO
O
NH2
NO
O
CH3COOH
ClCH2COOH
ClCH2CH2COOH
ClCH2CH2CH2COOH
ClCH2CH2CH2CH2COOH
FCH2COOH
Cl2CHCOOH
Cl3CCOOH
��-����*#(���������)��������-�"����
p.13 電気陰性度�
� � �
�
> <�����D/�>�S�EHFRN*���
"��MQRpKaN� �
9-7
���.� � Inductive Effect
/�
pKa
4.8
2.8
4.1
4.5
4.7
"
.� � ��+*������Delocalization of Negative Charge
by Inductive Effect
2.6
Cl CH2 C
O
O
1.3
0.7
OH OHO2N
OOO O
O
NO
O
O
NO
O
*9.5. *# ��"��������Electronic Effect
/��
pKa 10 7.2
%����!&$�(Canonical Formulae)
�' �������
����, � Resonance Effect
�������!&$�(Canonical Formulae) �
' �������
1.0�-"�pKa 4.6
/��NH2 NH2O2N
NH2
NO
O
NH2
NO
O
CH3COOH
ClCH2COOH
ClCH2CH2COOH
ClCH2CH2CH2COOH
ClCH2CH2CH2CH2COOH
FCH2COOH
Cl2CHCOOH
Cl3CCOOH
��-����*#(���������)��������-�"����
"��MQRpKaN� �
9-7
���.� � Inductive Effect
/�
pKa
4.8
2.8
4.1
4.5
4.7
"
.� � ��+*������Delocalization of Negative Charge
by Inductive Effect
2.6
Cl CH2 C
O
O
1.3
0.7
OH OHO2N
OOO O
O
NO
O
O
NO
O
*9.5. *# ��"��������Electronic Effect
/��
pKa 10 7.2
%����!&$�(Canonical Formulae)
�' �������
����, � Resonance Effect
�������!&$�(Canonical Formulae) �
' �������
1.0�-"�pKa 4.6
/��NH2 NH2O2N
NH2
NO
O
NH2
NO
O
CH3COOH
ClCH2COOH
ClCH2CH2COOH
ClCH2CH2CH2COOH
ClCH2CH2CH2CH2COOH
FCH2COOH
Cl2CHCOOH
Cl3CCOOH
��-����*#(���������)��������-�"����
"��MQRpKaN� �
9-7
���.� � Inductive Effect
/�
pKa
4.8
2.8
4.1
4.5
4.7
"
.� � ��+*������Delocalization of Negative Charge
by Inductive Effect
2.6
Cl CH2 C
O
O
1.3
0.7
OH OHO2N
OOO O
O
NO
O
O
NO
O
*9.5. *# ��"��������Electronic Effect
/��
pKa 10 7.2
%����!&$�(Canonical Formulae)
�' �������
����, � Resonance Effect
�������!&$�(Canonical Formulae) �
' �������
1.0�-"�pKa 4.6
/��NH2 NH2O2N
NH2
NO
O
NH2
NO
O
CH3COOH
ClCH2COOH
ClCH2CH2COOH
ClCH2CH2CH2COOH
ClCH2CH2CH2CH2COOH
FCH2COOH
Cl2CHCOOH
Cl3CCOOH
��-����*#(���������)��������-�"����
"��MQRpKaN� �
9-7
���.� � Inductive Effect
/�
pKa
4.8
2.8
4.1
4.5
4.7
"
.� � ��+*������Delocalization of Negative Charge
by Inductive Effect
2.6
Cl CH2 C
O
O
1.3
0.7
OH OHO2N
OOO O
O
NO
O
O
NO
O
*9.5. *# ��"��������Electronic Effect
/��
pKa 10 7.2
%����!&$�(Canonical Formulae)
�' �������
����, � Resonance Effect
�������!&$�(Canonical Formulae) �
' �������
1.0�-"�pKa 4.6
/��NH2 NH2O2N
NH2
NO
O
NH2
NO
O
CH3COOH
ClCH2COOH
ClCH2CH2COOH
ClCH2CH2CH2COOH
ClCH2CH2CH2CH2COOH
FCH2COOH
Cl2CHCOOH
Cl3CCOOH
��-����*#(���������)��������-�"����
Amino Acid α-qssr α-NH2 Side chain Alanine 2.35 9.87 Arginine 2.01 9.04 12.48 Asparagine 2.02 8.80 Aspartic Acid 2.10 9.82 3.86 Cysteine 2.05 10.25 8.00 Glutamic Acid 2.10 9.47 4.07 Glutamine 2.17 9.13 Glycine 2.35 9.78 Histidine 1.77 9.18 6.10 Isoleucine 2.32 9.76 Leucine 2.33 9.74 Lysine 2.18 8.95 10.53 Methionine 2.28 9.21 Phenylalanine 2.58 9.24 Proline 2.00 10.60 Serine 2.21 9.15 Threonine 2.09 9.10 Tryptophan 2.38 9.39 Tyrosine 2.20 9.11 10.07 Valine 2.29 9.72�
p.1136
p.1128
Uri8�:
Amino Acid α-qssr α-NH2 Side chain Glycine 2.35 9.78 �Glycine pKa1 = 2.35 pKa2 = 9.78
COOHA→ACOO- + H+
NH3+A→ANH2 + H+
p.1130 Amino Acid α-qssr α-NH2 Side chain Alanine 2.35 9.87 Aspartic Acid 2.10 9.82 3.86
COOHA→ACOO- + H+
NH3+A→ANH2 + H+
COOHA→ACOO- + H+
p.1130 Amino Acid α-qssr α-NH2 Side chain Aspartic Acid 2.10 9.82 3.86 Glutamic Acid 2.10 9.47 4.07
COOHA→ACOO- + H+
NH3+A→ANH2 + H+
COOHA→ACOO- + H+
p.1130 Amino Acid α-qssr α-NH2 Side chain Glutamic Acid 2.10 9.47 4.07 Glutamine 2.17 9.13
p.1130 Amino Acid α-qssr α-NH2 Side chain Glutamic Acid 2.10 9.47 4.07 Lysine 2.18 8.95 10.53
COOHA→ACOO- + H+
NH3+A→ANH2 + H+
NH3+A→ANH2 + H+
p.1131
l^d]z�
Vrcavw��
Amino Acid α-qssr α-NH2 Side chain Lysine 2.18 8.95 10.53 Histidine 1.77 9.18 6.10
p.1131 Amino Acid α-qssr α-NH2 Side chain Phenylalanine 2.58 9.24 Tyrosine 2.20 9.11 10.07
!+�lpIBIsoelectric pointm TaWjMLR�$�K X]WjMLR�$�N ��SPI��MEDJB +*�N����N +%�FoKLRtrNGKC�
p.1138 Uuhz
,>#
p.1137 l^d]zN3=$�
pK1=1.77, pK2=6.10, pK3=9.18
p.1139
[wbrz8
,>#
p.1139
v\z
,>#
Uri8N�=MHBI
p.1139
p.1140
+�����
p.1140
��Yie_ZfcU�
p.1143
p.1143
p.1148
ondgN�6K ��!MHBI
p.1153
p.1148
p.1149
���6
p.1149
-��|N�9/��
ondgD B%'}�~
p.1149
p.1150 ondgD B%'}�~
p.1150
p.1150
p.1150
p.1151
p.1152
p.1154 ondg/���N���(MHBI
p.1154 �5K"�
p.1154 �5�MHBI
http://www.ks.uiuc.edu/Research/smd_imd/pla2/�
ペプチド結合試薬について
p.1155 "��{0��
p.1155
ペプチドの合成戦略について
p.1153 ���(S�4GIPQC
ペプチド合成のための 固相法について
Dr. Robert Bruce Merrifield, 1984�Mbkdg� '���
p.1157 *!MQRondg��
ポリペプチドの１次構造について ポリペプチドの２次構造について ポリペプチドの３次構造について
Asp-Phe�
L-Asp + L-Phe
L-Asp-L-Asp�L-Asp-L-Phe L-Phe-L-Asp L-Phe-L-Phe�
Asp-Phe�
DL-Asp + DL-Phe
L-Asp-L-Asp�L-Asp-L-Phe L-Phe-L-Asp L-Phe-L-Phe�
D-Asp-D-Asp�D-Asp-D-Phe D-Phe-D-Asp D-Phe-D-Phe�
L-Asp-D-Asp�L-Asp-D-Phe L-Phe-D-Asp L-Phe-D-Phe�
D-Asp-L-Asp�D-Asp-L-Phe D-Phe-L-Asp D-Phe-L-Phe�
L-Asp-L-Asp�L-Asp-L-Phe L-Phe-L-Asp L-Phe-L-Phe�
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